DE2151737A1 - Synthetic rubber compounds - Google Patents

Description

The invention relates to synthetic rubber compositions with a content of thermoplastic resin to increase the tack.

Synthetic rubbers such as styrene-butadiene rubber, alfin rubber, isobutylene-isoprene rubber, butadiene rubber, Chloroprene rubber and acrylonitrile butadiene rubber are only slightly tacky compared to natural rubber, so that generally means for increasing the tackiness can be used to improve the properties of the rubber during processing on the calender and the adhesiveness to increase the adhesive surfaces in the production of layered materials or laminated products. As such "tackifiers" So far, among other things, alkylphenol resins such as alkylphenol-acetylene condensates and alkylphenol-formaldehyde condensation products were known and alkyl phenol sulfide resins Xylene resins, coumarone-indene resins, petroleum resin and the like.

Of these additives, alkylphenol resins and xylene resins show have a relatively good tackifying effect, but have the disadvantage of a very high price. Coumarone-indene resins are relatively cheap, but their effect is much less than that of the two types of resin mentioned above. Petroleum resins Similar to coumarone-indene resins, they are very ineffective.

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BATH ORIGINAL

An additive serving to increase the tackiness may affect the other physical properties of the finished synthetic rubber compound not affect. If the rubber compound is to be vulcanized, it is also important that the vulcanization time is not unduly elongated by the addition of the tackifier.

The object of the invention is to provide compositions of synthetic rubber and thermoplastic resin which are excellent Have tackiness and are free from the above-mentioned drawbacks of synthetic rubber that with conventional ones Additives made sticky.

This object is achieved according to the invention by a rubber compound, containing 3-30 parts by weight of phenol-modified resin per 100 parts by weight of a synthetic rubber, the was obtained by polymerizing 100 parts by weight of a hydrocarbon mixture having a boiling range of 140 - 280 C and has unsaturated, when cracking petroleum contains hydrocarbons occurring as a by-product, and 3-15 parts by weight of a phenolic compound, using 0.05-5 parts by weight of boron trifluoride, one Boron trifluoride complex compound or aluminum chloride as Catalyst.

The synthetic rubber composition according to the invention can be produced industrially at low costs. Crowds after the Invention are also effective as adhesives for paper, wood and other natural substances as well as synthetic ones High polymers.

Starting materials for the preparation of the tackifiers according to the invention are a cracked oil fraction with a boiling range from 140 - 280 C or mixtures of subfractions in suitable Ratios are put together and within

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of the boiling range mentioned have been fractionated from a hydrocarbon oil, which is used as a woven product in Cracking of petroleum and the like, e.g., thermal cracking such as steam cracking, thermal cracking Cracking in the steam phase, in sand cracking or catalytic cracking, etc., to produce ethylene, propylene, butenes, butadienes and the like, using light or Heavy naphtha, kerosene or light oil, heavy or Crude oil etc.

A fraction obtained in this way with a boiling range of 140 280 C contains styrene, indene and indene derivatives in large quantities Amounts. If a fraction below 140 is used, the softening point of the resin produced is lowered, and the physical properties such as tensile strength, tensile stress, etc. are also reduced when a rubber compound using such a resin.

As the phenol or phenolic substance, phenol, cresol, xylenol, tert-butylphenol, nonylphenol and the like can each be used alone or as a mixture of two or more components. Suitable additional amounts are 3-15% by weight, based on on the crack oil fraction.

The resin obtained with an addition of less than 3% phenol or phenolic compound to the cracked oil fraction does not give excellent adhesiveness when incorporated into synthetic rubber as described below Comparative example shows. A resin made with 15% or more of phenol or phenolic compound however, shows the tendency to vulcanize the with to delay spiked synthetic rubber. The catalyst used is that of the ordinary Friedel-Craft type used, especially boron trifluoride complex compound or aluminum chloride in an amount of 0.05-5% by weight, based on the starting material used oil.

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The manufacture of resins for the purposes of the invention can be carried out as follows:

A cracked oil fraction and phenol or phenolic compound (s) are introduced into the specified fixed ratio to a reaction vessel, with the addition of the catalyst and at a temperature of 0 - 8O ⁰ C and stirred for 1-5 hours brought to implementation. After the reaction has ended, the resin is recovered by decomposing the catalyst with acid or alkali, washing the product with water and removing the proportion of unreacted oils and low polymers by evaporation or distillation.

The hydrocarbon resin thus obtained has a softening point of 50-120 ° C (measured according to JISK 2531-60) and a Color of 3-4 according to the Gardner color scale (ASTMD 1544-58T, measured on a solution of 2 g of resin in 25 ml of benzene).

Hydrocarbon resins in the manner described with Phenol or modified phenolic compounds are suitable as tackifiers for synthetic rubber, as they are when incorporating into the most varied types of synthetic rubber give them excellent adhesiveness.

The new resins can be added to the synthetic rubber along with conventional tackifying agents will.

To make the composition of the invention, a synthetic rubber and the tackifier described above are used compounded by blending. To increase the adhesive strength of the binding surfaces during processing of synthetic rubber, preferably 3 to 30 parts of tackifier per 100 parts of synthetic rubber are used. If less than 3 parts are added, the

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Improvement of the tackiness insufficient, while with more than 30 parts the physical properties of the synthetic Rubber can be affected. However, a larger proportion can be used to produce adhesives for paper, wood, synthetic high polymers and the like can be used.

Synthetic rubber compositions according to the invention not only show the surprising feature of extremely high adhesive strength, but also also have advantages in terms of physical properties of synthetic rubber are favorably influenced and not impaired, no delay in vulcanization takes place, etc.

As the main starting material for those used as tackifiers When new resins in the petrochemical industry are produced in large quantities, they can be controlled in a controlled manner Produce quality and at low cost, which is not least a major advantage.

Production methods for phenol-modified coumarone-indene resins and for petroleum resins are in Japanese patent publications as described in 39-24275 and 45-8163. The first concerns the production of alcohol-soluble coumarone-indene resin, while the second treats resins intended to serve as sizing agents. So the purpose is very different than in the case of the invention, which involves the production of resins for incorporation into synthetic rubber, and accordingly, the properties required of resins suitable therefor also show the following significant deviations:

Since Japanese Patent Publication 39-24275, as said, the production of alcohol-soluble resin aims, the amount of phenol that can be used is not limited - the Rather, the solubility of the resin improves when the proportion of phenol or phenolic compound is increased. In the opposite

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This can be set in the case of resins for synthetic rubber compounds according to the invention, if the addition of phenol is increased, some undesirable effects occur, e.g. a reduction in the vulcanization rate when vulcanizing the with synthetic rubber added to the resin. For this reason, the upper limit is set for the amount of phenol to be used been.

Japanese Patent Publication 45-8163 describes Resins that have an acid number of 100 - 170 and are intended for use in sizing agents. The resins for the invention On the other hand, purposes are achieved through copolymerization of the starting oil "Obtained with 3-15% phenol or phenolic compound and show precisely because of this certain proportion of phenol or the like. an excellent effect when in the synthetic Rubber can be incorporated.

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

A fraction with a boiling range of 140-180 ° C, which is obtained from the steam cracking of naphtha Cracked oil had been cut, contained 55% polymerizable fractions. This fraction was used as the starting material and after adding 5% phenol or phenolic compound (based on the starting material) using Polymerized by 0.5 wt.% Boron trifluoride-ethyl ether complex as a catalyst at 30 ° C for 3 hours. After decomposing of the catalyst with aqueous sodium hydroxide solution, the resin was unreacted by washing with water and removing Oils obtained by evaporation under vacuum. The type of phenol used, the yield and properties of the obtained resins are shown in Table 1. For comparison, the values for resin without the addition of phenol or phenolic compound indicated.

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Table 1

No. Type of added properties of the resin

Phenol Yield Softener P. Acid number color

1 phenol 34% 85 ° C 59 4th 2 Cresol ⁺ 35% 80 ° C 50 4th 3 p-tert-butylphenol 42% 99 ° C 49 4th 4th Nonylphenol 40% 99 ° C 45 3 See.
ex . no 42% 110 ° C 0 3

Gas chromatographic analysis of the cresol:

phenol 30th o-cresol 10 m-cresol 25th p-cresol 15th XylenoI 10

These resins were made as well as commercially available alkylphenol-formaldehyde resin and commercial coumarone-indene resin as The tackifier is mixed with styrene-butadiene rubber in the ratio shown in Table 2, and the Samples were tested for stickiness, viscosity and scorch behavior according to Ilooney, and examined for the rate of vulcanization.

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Table 2

Styrene-butadiene rubber (JSR # 1500) 100 parts by weight

Zinc Oxide No. 1 5 ^{! I}

Stearic acid 2 "

Sulfur 2

Accelerator DM 1.5 "

Accelerator TT 0.2 "

Soot HAP (ceased H) 50 "

Softener iSurcolite process oil) 4 "

Tackifier 5 "'

For compounding all the components of the mixture formulation were worked in addition to the tackifiers on the roll mill, the Oberflächenterperatur the rolls to 5O + _ 5 C was maintained, and then each tackifier was rolled, the surface temperature of the rollers in each case 5 C above the softening point of the relevant additive would be held. The rolls had a diameter of 200 mm and a width of 450 rim; at a gear ratio of 1:18, the front roller ran at 13 rpm. Each of the above test batches was then rolled out at a roller surface temperature of 55-60 ° C. for 3 minutes to form a plate approximately 3 mm thick. These plates were left to stand at 21 ° C. for about 3 hours, and then the adhesive strength was determined with the pick-up tackmeter, with a pressure of 10 seconds. under a load of 500 g. The results of the experiments are shown in Table 3. The left Kr. 1-4 are those with tackifier according to the invention. The information is supplemented by the comparative example given above and the values for commercially available alkylphenol resin and commercially available coumarone-indene resin.

209822/0979 BATH ORIGINAL

Tabel

Tackifier no. 1 no. 2 no. 3 no. 4 Cf.

ex. Alkylphenol resin Cuniaron - Inden-IIarz

Adhesion 380 850 760 830 800 400 810

380 850 760 830 800 400 100 224 200 218 210 105

Index ⁺ 100 224 200 218 210 105 213

KJ O CO

J ^ ⁺ The index in the table is the relative adhesive strength

¹ ^ of the product in question specified / based on that of the

ο tackifier-free mass, which was set equal to 100

As can be seen from the table above, compositions containing styrene-butadiene rubber and tackifier according to the Invention contain a much higher adhesiveness than those with coumarone-indene resin and even the same or even more higher adhesiveness than those with alkylphenol resin. Even a composition containing resin without phenol or phenolic compounds as an additive has much lower adhesiveness as such with resin into which phenol or a phenolic compound had been introduced.

The samples were tested for Mooney scorch behavior in accordance with JISK 6 300-1063. The test results are shown in Table 4. An L-shaped rotor was used in the test and the test temperature was 120 ° C with 1 minute preheating time.

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P O

Table 4

Type of no No 1 Ur. 2 No. 3 Kr.4 Cf. commercially available commercially available tackifier example. Alkylphenol coumarone indene

Resin resin

i> looney viscosity

(120 °) 63 56 57 57 57 57 56

maximum

Mooney viscosity 69 62 63 63 63 63 61

"*" - · -looney tfbervulka-

Jx nization time

t5 14'04 ^; '1β'24 "16Ί1 ¹¹ 15'2O"15'2O"12" 38 ^{! L}

* t35 19'29 "21'54"21'32"20'54"21'42"20'58"

tA3O 5'25 '"5'3O" 5 ¹ Il "5'3I"6'22"5'20"

12th • 13 " 15th • 42 " 17th • 26 " 22nd • 31 " 5 Ί8 " 6th • 49 "

N) -λ cn

> <! CO

As can be seen from Table 4 above, there are os with regard to the Mooney overcure time no significant Difference between the wet ones according to the invention of styrene-butadicn rubber with tackifier on the one hand and the tackifier-free masses on the other hand, which indicates that there will be no significant difference between the two in the vulcanization time either.

The samples were then vulcanized according to the method of ASTf ID 15-64'J ^{1 for} 20 and 40 minutes at 150 ° C, and the physical properties of the vulcanizates were determined according to the specification of JISK G301-196 3. Ks were the following sub ψ searching condition applied:

Tensile test: Schopper tearing machine (capacity "30 kg) Pulling speed 5 (JO imn / min

I test body iJLab type no.3
Shepherd's examination: spring measuring device
Rough temperature: 2'j C

The results obtained are shown in Table ΰ below shown.

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N to VO w r-i in Φ «Tf r-t r-i .α SJ ο I. -H r-l r-t O -Q Γ4 CO .Ει r-t Oil ω • Γ * > | pj Ai (β r-t

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vo vo

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approx • rf

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AA CM B. ehnu approx -H ο Q tn Φ Ai Ai Ό fr φ O ■ Η H Sc CM 11 'eat M. dp Ö Φ
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O X co N

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It can be seen from Table 5 above that the compositions contain styrene-butadiene rubber compounds + tackifier according to the invention and the mixture without any tackifier in the vulcanization speed and in the physical Properties of the vulcanizates do not differ significantly. The tackified mixture according to the invention was also found to be used far superior to the mixture containing alkylphenol resin.

Example 2

A fraction having a boiling range of 170 - 22O ° C _f ψ at which a steam-cracking of naphtha cracking oil fraction obtained had been removed contained 65% by weight of polymerizable components.. This fraction was used as starting material and, after addition of 9 parts of phenol, polymerized under the same conditions as in Example 1. The properties of the resins obtained are shown in the table below.

Table 6

No. Type of added properties of the resin

Phenol Yield Softening P-Acid Value Color . 5 phenol 45% 60 ° C 78 4

"6 cresol ⁺ 45% 68 ° C 70 4

7 p-tert-butylphenol 5O% 70 ° C 52 4

8 Nony! Phenol 46% 78 ° C 56 3

For the composition of the cresol see table 1

Alfin rubber was made on the roller mill with these resins or with commercially available alkylphenol-formaldehyde resin as Tackifier following the mix recipe of

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Table 7 mixed. The samples are checked for adhesive strength tested and subjected to vulcanization tests. The test results are shown in Tables 8 and 9. the Samples: ir. 5-8 were masses according to the invention. When meddling the surface temperature of the rollers was kept at 100 + 5 ° C; Compounding and investigation took place following the same procedure as described in Example 1.

Table 7

Alfin-Kautachuk [PA) / W = 85/15)

Zinc Oxide # 1

fJsulphur

Accelerator C 2

Kiss UAF (ceased H)

Verification agent (Sandeχ 58) Tackifier

100 r, possibly ficht s parts 2 ti 2 Il 2 , 3 ti 1 , 4 II

3O

Table ü

Klebrigniacher commercial o.s. no No. 5 ι Jr. 6 No. '. 7 No. 8 AlAy! Phenol resin

Adhesion strength (g) 240 440 44o 4OO 880 index 100 183 183 107 158

470 V) ¹ y

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BATH ORIGINAL

Table 9

300% modulus Vulcanization no No. 5 Tackifier No. 7 No. 8 commercially available kg / cm time (min) 111 88 No. 6 90 91 Alkylphenol resin 20th 116 97 86 96 96 80 tensile strenght 40 96 83 O kg / cm 220 212 208 208 co
00 Strain, % 20th 220 205 210 211 207 207 NJ
NJ 40 510 550 220 570 560 216 O
CO Hardness, Hs 20th 500 530 580 550 550 630 CO 40 59 56 570 57 56 600 20th 60 58 56 . 57 58 54 40 59 56

As can be seen from Table 8, the adhesive strength of the tackifier according to the invention is almost equal to that of commercially available alkylphenol resin. From table 9 it can be seen that the tackifier-containing composition according to the invention gives better results in the vulcanization tests than Compounds containing commercially available alkylphenol resins.

Example 3

The same fraction as in Example 1 was mixed with 7 parts of phenol or phenolic substance using boron trifluoride gas and aluminum chloride as a catalyst polymerized at 50 ° C. for 1 hour. Subsequently, the reaction product was described in the same manner as in Example 1 treated. The properties of the resins obtained are shown in Table 10:

Table 10

No. Type of tensile - Catalyst Properties of the resin

put phenol type% yield softening p. Acid color

9 phenol BF ₃ -GaS 0 / 3 40% 80 ° C 60 4th 10 Cresol ⁺ AlCl ₃ 1 43% 8 3 ° C 60 4th 11 Nony! Phenol AlCl ₃ 1 , 0 40% 85 ° C 55 4th

for the composition of the cresol see table 1

A mixture of styrene-butadiene rubber and butylene rubber was made on the roll mill with these resins as well as with commercially available alkylphenol-formaldehyde resin or commercially available coumarone-indene resin, if applicable of the formulation of Table 11 and the products were tested for adhesive strength.

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Table 11 70 parts by weight Il Styrene-butadiene rubber (JSR No. 1500) 30th Il Butylene rubber (JSR BR-Ol) 5 Il Zinc Oxide No. 1 2 Il Stearic acid 2 If sulfur 1/5 It Accelerator DM 0.2 If Accelerator TT 50 Soot HAF

Softener (Surcolite process oil) 4 "

Rolling in was carried out in the same manner as in Example 1. The adhesive strength was also determined as in example 1; the test results are shown in Table 12.

Table 12

Tackifier commercial commercial

no no 9 no 10 _Nrai alkylphenol resin coumarone

Indene resin

Adhesion strength 60 180 22O 21O 22O 150

Index 1OO 300 367 35O 367 250

As can be seen from Table 12, the Masses containing the tackifier and the mixture of styrene-butadine rubber and butylene rubber contain, in terms of their adhesive strength, the tackifier-free compositions as well as superior to the masses with coumarone-indene resins and about as good as the compounds with alky! phenol resins.

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Comparative example 1

The same fraction as in Example 1 was with 2% phenol or phenolic compound (based on this fraction) using, of 0.5 wt.% Boron trifluoride-ethyl ether complex Polymerized as a catalyst for 2 hours at 50 ° C. After the completion of the reaction, the catalyst was washed with aqueous Sodium hydroxide solution is decomposed and the resin obtained is washed with water and unreacted by vacuum distillation oil free. The type of phenol used, as well as the yield and properties of the resins produced are summarized in Table 13.

Table 13

No. Type of tensile properties of the resin

put phenol _Yield softener. P. Acid number color

12th phenol 42% 96 ° C 31 3 13th p-cresol 40% 95oC 26th 3 14th p-tert-butylphenol 40% 103oC 20th 3 15th Nony! Phenol 41% 103 ° C 20th 3

The resins were mill mixed in following the recipe of Example 1 and the products were exposed checked their adhesive strength. The test results are shown in Table 14.

Table 14

Tackifier no # 12 # 13 # 14 # 15

Adhesive strength 350 470 480 430 460 index 100 134 137 123 131

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As can be seen from this table, the adhesive strength is These resins are so insignificant that they can scarcely develop a similar effectiveness as tackifiers as those after Resins obtained in Example 1.

Comparative example 2

The same fraction as in Example 1 was polymerized with 20 parts of phenol or phenolic compound using 0.5% by weight of boron trifluoride-ethyl ether complex as a catalyst at 10 ° C. for 5 hours. After the end of the reaction, the catalyst was decomposed with aqueous sodium hydroxide solution, and ψ the resin obtained was washed with water and freed from unreacted oils by vacuum distillation. Table 15 shows the type of phenol used in each case and the yield and properties of the resins produced in this way.

Table 15

No. Type of tensile properties of the resin

put phenol Yield softener. P. Acid number color

16 phenol 42% 62 ° C 145 4th 17th p-cresol 43% 60 ° C 133 5; 13th p-tert-butylphenol 40% 65 ° C 110 4th 19th Nony! Phenol 42% 65 ° C 105. 5

These resins were made following the blend recipe of Example 1 incorporated on the roller mill, and the product passed the adhesive strength test and deni IIooney scorch test subject. The results obtained are in the following Tables 16 and 17 'to s poor η formulated τ

0 5P Zu / O ₉₇ *. BADORIG.NAL

Table 16

Tackifier No Mr.16 No.17 No.18 No.19

Adhesive strength 380 850 800 800 780 index 100 224 210 210 205

Table 17

Tackifier no # 16 # 17 # 18 # 19

Mooney viscosity

63

Mooney over-vulcanization time

t5 14Ό4 "21'2O" 21'45 "21Ό4" 21Ό8 "

t35 19'29 "27'37" 28'37 "28'32" 27'35 "

TA 35 5'25 "6Ί7" 6'52 "7'28" 6'32 "

As can be seen from Tables 16 and 17 above, the adhesive strength when incorporated into rubber is the same that of Example 1, however, there is a tendency for the vulcanization time to be considerably increased.

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Claims (3)

Claims 1. Synthetic rubber masses with a content of thermoplastic Resin for increasing tack, characterized in that it is synthetic per 100 parts by weight Rubber 3 contain 30 parts by weight of phenol-modified resin obtained by polymerizing 100 parts by weight a hydrocarbon mixture which has a boiling range of 140-280 C and is unsaturated when cracking Hydrocarbons produced as a by-product of petroleum * contains, and 3-15 parts by weight of a phenolic compound using 0.05-5 parts by weight of boron trifluoride, a boron trifluoride complex compound or aluminum chloride was obtained as a catalyst. 2. Composition according to claim 1, characterized in that it is styrene-butadiene rubber, alfin rubber, isobutylene-isoprene rubber, Contains butadiene rubber, chloroprene rubber and / or acrylonitrile butadiene rubber. 3. Composition according to claim 1, characterized in that the phenolic compound is phenol, cresol, xylenol, tert-butylphenol or Nony! phenol. 209822/0979